We propose and experimentally demonstrate a novel scheme to realize polarization-division-multiplexing quadrature-phase-shift-keying (PDM-QPSK) signal transmission over fiber, wireless and fiber at W-band (75-110 GHz). The generation of polarization multiplexing millimeter-wave (mm-wave) wireless signal is based on the photonic technique. After 20-km fiber transmission, polarization diversity and heterodyne beating are implemented to convert the polarization components of the polarization-multiplexing signals from the optical baseband to W-band so that up to 16 Gb/s mm-wave signals can be delivered over 2-m 2×2 multiple-input multiple-output (MIMO) wireless link. At the receiver base station (BS), polarization combination reconstructs the PDM-QPSK signal which is then launched into another 20-km fiber. In the experiment, coherent detection is introduced to improve receiver sensitivity and constant modulus algorithm (CMA) is applied for polarization de-multiplexing. The bit-error-ratio (BER) for 16-Gb/s PDM-QPSK signal delivery is below the forward-error-correction (FEC) threshold of 3.8×10-3 with the optical signal-to-noise ratio (OSNR) above 11.8 dB.